WO2001085333A2 - An apparatus for the controlled optimized addition of reactants in continuous flow reaction systems and methods of using the same - Google Patents

An apparatus for the controlled optimized addition of reactants in continuous flow reaction systems and methods of using the same Download PDF

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Publication number
WO2001085333A2
WO2001085333A2 PCT/CA2001/000613 CA0100613W WO0185333A2 WO 2001085333 A2 WO2001085333 A2 WO 2001085333A2 CA 0100613 W CA0100613 W CA 0100613W WO 0185333 A2 WO0185333 A2 WO 0185333A2
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Prior art keywords
reaction zone
fluid
tubular
reaction
reactant
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PCT/CA2001/000613
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English (en)
French (fr)
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WO2001085333A3 (en
Inventor
Alaa Eldin Mostafa Adris
Fahad A. Al-Sherehy
Mustafa A. Soliman
Tarique Hakeem
Shickh Kareemuddin
Abdullah A. Al-Nutaifi
Munawwar Saudagar
Shahid M. Azam
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Saudi Basic Industries Corporation
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Application filed by Saudi Basic Industries Corporation filed Critical Saudi Basic Industries Corporation
Priority to KR1020027014849A priority Critical patent/KR100742842B1/ko
Priority to AT01931244T priority patent/ATE468914T1/de
Priority to DE60142229T priority patent/DE60142229D1/de
Priority to EP01931244A priority patent/EP1284815B1/en
Priority to AU2001258079A priority patent/AU2001258079A1/en
Publication of WO2001085333A2 publication Critical patent/WO2001085333A2/en
Publication of WO2001085333A3 publication Critical patent/WO2001085333A3/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/26Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006Controlling or regulating processes
    • B01J19/0013Controlling the temperature of the process
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J19/0006Controlling or regulating processes
    • B01J19/002Avoiding undesirable reactions or side-effects, e.g. avoiding explosions, or improving the yield by suppressing side-reactions
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J19/24Stationary reactors without moving elements inside
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    • B01J19/24Stationary reactors without moving elements inside
    • B01J19/2415Tubular reactors
    • B01J19/2425Tubular reactors in parallel
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    • B01J19/24Stationary reactors without moving elements inside
    • B01J19/2415Tubular reactors
    • B01J19/244Concentric tubes
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/065Feeding reactive fluids
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J8/02Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/067Heating or cooling the reactor
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J8/18Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1818Feeding of the fluidising gas
    • B01J8/1827Feeding of the fluidising gas the fluidising gas being a reactant
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J8/18Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/26Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • B01J2208/00168Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00212Plates; Jackets; Cylinders
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • B01J2208/00168Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00212Plates; Jackets; Cylinders
    • B01J2208/0023Plates; Jackets; Cylinders with some catalyst tubes being empty, e.g. dummy tubes or flow-adjusting rods
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • B01J2208/00168Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00256Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles in a heat exchanger for the heat exchange medium separate from the reactor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/0053Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00539Pressure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00548Flow
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J2219/00002Chemical plants
    • B01J2219/00027Process aspects
    • B01J2219/00033Continuous processes
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00051Controlling the temperature
    • B01J2219/00074Controlling the temperature by indirect heating or cooling employing heat exchange fluids
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J2219/00049Controlling or regulating processes
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    • B01J2219/00259Preventing runaway of the chemical reaction
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00245Avoiding undesirable reactions or side-effects
    • B01J2219/00259Preventing runaway of the chemical reaction
    • B01J2219/00263Preventing explosion of the chemical mixture

Definitions

  • the present invention relates to an improved continuous flow chemical reaction apparatus wherein the introduction of at least one reactant feed into the reaction zone is optimized.
  • the invention also relates to improved chemical reactions achieved using the continuous flow chemical reaction apparatus. Description of Related Art
  • An oxidative dehydrogenation, or partial oxidation, process is a one step conversion of light hydrocarbons to olefins and carboxylic acids.
  • the process potentially offers many advantages over cracking and pure dehydrogenation which are extremely capital intensive and energy intensive.
  • the conversion of saturated hydrocarbons into olefins and carboxylic acids over low temperature catalysts was disclosed by Thorstienson et al. in a report published in Journal of Catalysis, vol. 52, pp. 116-132 (1978).
  • U.S. Patent No. 4,250,346 discloses a process for oxidative dehydrogenation of ethane to ethylene suggesting different low temperature catalyst systems.
  • European Patent No. EP 0 518 548 A2 discloses a process for making acetic acid which comprises oxidizing ethane with molecular oxygen in a reaction zone at a pressure at least 100 psig while the reactants are in contact with a solid catalyst containing vanadium and phosphorous oxides (VPO system).
  • VPO system vanadium and phosphorous oxides
  • U.S. Patent No. 4,899,003 issued to Union Carbide relates to multi-staging the reactor system where a feed gas comprising ethane and oxygen is converted over an oxydehydrogenation catalyst to a product gas comprising ethylene, acetic acid, water, ethane, and carbon oxides.
  • the product gas from each stage (other than the last stage) is cooled and a portion of the acetic acid and water is separated and oxygen is added before passing the product gas stream to the next reaction stage.
  • Total oxygen content in the feed stream to any of the reactors was maintained below 6 mole percent with respect to the total input gaseous stream in that stage.
  • U.S. Patent No. 5,583,240 issued to SRI relates to a reactor with porous membranes to provide for the continuous addition of one reactant all along the reactor and mixing in the entire volume of the reactor to minimize or eliminate local high concentration gradients and hot spots.
  • the other reactant is flowed through the inside of the permeation tube, which contains mixing elements. Those mixing elements were claimed to increase the yield of
  • European Patent No. EP 546 677 Al relates to a fluidized bed for ethane oxidation to acetic acid.
  • the disclosed process included three key steps: (1) cooling the gaseous effluent from the reaction zone; (2) separating most of the acetic acid in liquid form from the effluent gases, leaving a gaseous stream containing nearly all of the carbon oxide contained in the effluent; (3) purging a small portion of said gaseous stream and recycling most of the gaseous
  • Purging is intended to prevent build-up of carbon oxides in the reaction zone, while recycling serves to maintain a high proportion of carbon oxides in the reaction zone gases, thus aiding in moderating the temperature elevating effect of the highly exothermic oxidation reaction.
  • U.S. Patent No. 5,723,094 relates to a chemical reactor design which provides improved micro-mixing conditions and reduced localized zones of concentration to increase reaction selectivity to desired products.
  • the design includes a capillary tubelet positioned within and along the length of flow tubes positioned in a shell reactor and one or more distributors for distributing a first reactant into the flow tubes and a second reactant into the capillary tubes.
  • European Patent Publication No. 0 532 325 relates to a method and apparatus for the production of ethylene oxide.
  • European Patent Publication No. 0 383 224 relates to a shell- and-tube reactor and method of using the same.
  • the present invention relates to a process and apparatus for the controlled/optimized addition of reactant(s) in continuous flow chemical reactions, preferably oxidative dehydrogenation, partial oxidation, or oxidation reactions. More specifically, the invention deals with the shortcomings of these high potential processes by the controlled addition of a reactant which is achieved by means of an injection member (tube) along the length of the reaction zone.
  • the injection member (tube) is provided with injector(s) capable of introducing a controlled amount of reactant at the injector site into the reaction zone.
  • the injection member (tube) is provided with wall penetrations, holes, perforations, spargers, capable of performing two functions: (1) pressure drop control and (2) flow control.
  • the injectors allow for the introduction of a controlled amount of reactant into the reaction zone without allowing any reactant(s) to flow into the injector member (tube) from the reaction zone.
  • the present design offers a high degree of controllability over the quantity of reactant injection and the locations of the points of injection by adjusting the distance between the injection points. Therefore, injection can be optimized in such a way that only the sufficient and kinetically required amount of reactant is supplied at each point and this is controlled to respond to the spatial variation of the reaction conditions (i.e., temperature, pressure and
  • an intermediate or co-feed may be injected which enhances catalyst performance or suppresses a certain poisoning effect. This provides yet another utility of the present invention.
  • the benefits achievable by using the present invention include the accurate control of the temperature profile along the catalyst bed by controlling the reaction extent and heat release via the quantitative and positional control of reactant addition.
  • the invention also enhances the catalyst productivity by introducing reactants in proportions which are not possible in conventional reactors due to the explosion regime limitation and the reaction runaway limitation.
  • the invention also provides a tool for designing the reaction in such a way that the production of the desired product is optimized.
  • the invention also allows for the adjustment of the reactant mixture composition at every point inside the reactor, as well as the reactor entrance, so that reactant mixtures within the explosion regimes can be avoided.
  • the invention improves catalyst performance by the delayed addition of a component which reverts its reduction/oxidation state or a component which remedies a catalyst poisoning situation.
  • FIG. 1 is a schematical representation of an improved reaction zone according to
  • Figure 2 is a schematical representation of an improved reaction zone according to another embodiment of the invention.
  • Figure 3 is a schematical drawing of a reaction system according to one embodiment
  • Figure 4 is a schematical drawing of a reaction system according to another embodiment of the invention.
  • Figure 5 is a schematical drawing of a reaction system according to yet another embodiment of the invention.
  • Figure 6 is an enlarged schematical drawing of the pressure drop control means shown in Figure 5.
  • Figure 7 is a schematical drawing of a reaction system according to another embodiment of the invention.
  • Figure 8 is a schematical drawing of a reaction system according to yet another embodiment of the invention.
  • Figure 9 is a schematical drawing of a reaction system according to another embodiment of the invention.
  • Figure 10 is a graphical representation of the oxygen distribution pattern for a continuous flow chemical reaction zone according to one embodiment of the invention where the vertical axis represents oxygen flow (SLPH) and the horizontal axis represents the reaction tube coordinate along the length of the reaction zone (m).
  • SLPH oxygen flow
  • m reaction tube coordinate along the length of the reaction zone
  • Figure 11 is a graphical representation of the reaction temperature profile for a continuous flow chemical reaction zone according to one embodiment of the invention and according to two comparative continuous flow chemical reaction zones where the vertical axis represents reaction temperature ( °C) and the horizontal axis represents the reaction tube
  • Figure 12 is a graphical representation of the oxygen concentration profile for a continuous flow chemical reaction zone according to one embodiment of the invention and according to two comparative continuous flow chemical reaction zones where the vertical axis represents oxygen concentration ( mole %) and the horizontal axis represents the reaction tube coordinate along the length of the reaction zone (m).
  • Figure 13 is a schematical drawing of a reaction system according to another embodiment of the invention.
  • One aspect of the invention relates to improved continuous flow reaction systems.
  • One preferred embodiment of the invention relates to multi-tubular fixed bed catalytic reactors with the novel feature of a non-uniform distribution member such as the one described in Figure 1.
  • the first reactant feed is fed into a reaction zone via an inlet at one end of the reaction zone, while the second reactant feed is introduced into the reaction zone at a multiplicity of points along the length of the reaction zone via a central tube or distribution member.
  • the distribution member preferably satisfies two important criteria at each point along the length of the catalyst bed: (1) pressure drop control; and (2) flow control.
  • FIG. 2 shows a continuous flow chemical reaction apparatus 10 comprising a reaction zone 11, preferably a tubular reaction which optionally contains catalyst 12.
  • Reaction zone 11 also having a length and having a first fluid reactant feed inlet 13 for introducing first fluid reaQtant feed 14 into tubular reaction zone 11 at a first end 17 and a product outlet 15 for product stream 16 at a second end 18.
  • the first fluid reactant feed 14 comprises the first fluid reactant and, preferably, a portion of second fluid reactant.
  • the tubular reaction zone 11 also includes an interior conduit 20 extending lengthwise within tubular reaction zone 10. Conduit 20 having
  • a second feed inlet 21 for introducing a second fluid reactant feed (e.g., containing a second
  • Conduit 20 also having a multiplicity of injectors 30
  • conduit 20 may pass through the entire length of tubular reaction zone 11. Alternatively, conduit 20 may end within tubular reaction zone 11 (see Figure 3 described below).
  • the second fluid reactant is advantageously mixed with the first fluid reactant in the first fluid feed 14 so that an injector 30 is not required in the first segment of reaction zone 11.
  • the composition containing the second reactant provided in the first fluid feed may be the same or different from the composition containing the second reactant provided by the second feed.
  • the first feed may include pure oxygen (which is an oxygen-containing composition) as the second reactant and the second feed may contain air (which is also an oxygen-containing composition) also as the second reactant.
  • the first and second feed may contain the same second reactant composition such as each containing air or pure oxygen.
  • first fluid reactant feed 14 includes the first reactant (without any second reactant) and second fluid reactant feed 22 includes the second reactant.
  • the apparatus preferably includes an injector 30 proximate the first end 17 of the reaction zone 11 to provide second reactant at the front end of the reaction zone.
  • a continuous flow chemical reaction apparatus 40 comprising a plurality of tubular reaction zones 11, optionally containing catalyst 12, within a heat transfer vessel 41 including at least one heat transfer zone 42, each of the heat transfer zones 42 having a heat transfer fluid inlet 43 and a heat transfer fluid outlet 44.
  • Reactor apparatus 40 also having a first reaction feed inlet 45 for first reaction feed 14.
  • Reactor apparatus 40 also having a second reaction feed inlet 47 for a second reaction feed 22 and a reactor product outlet 46 for product stream 16.
  • first reaction feed 14 contains a first reactant (e.g., ethane, ethylene) and preferably a portion of a second reactant (e.g., air, oxygen).
  • first reactant e.g., ethane, ethylene
  • second reactant e.g., air, oxygen
  • Each of tubular reaction zones 11 having a length, a first fluid reactant feed inlet 13 at a first end, a product outlet 15 at a second end and an interior conduit 20 extending lengthwise within tubular reaction zone 11.
  • Interior conduits 20 having a multiplicity of injectors 30 spaced apart along the length of the conduits 20 and along the length of the tubular reaction zone 11 and each of injectors 30 being adapted to introduce a controlled amount of second fluid reaction feed 22 into tubular reaction zones 11.
  • heat transfer vessel 41 comprises a plurality of heat transfer zones 42.
  • heat transfer vessel 41 is a cylindrical vessel.
  • the continuous flow chemical reaction apparatus 40 of Figure 3 has interior conduits 20 which do not dead end in tubular reactor zone 11 but rather extend through tubular reaction zone 11 to outlet header 48 to exit the reaction apparatus 40 through second reactant feed outlet 49.
  • second feed exit stream 25 (containing excess, unreacted second reactant) can be passed through reaction apparatus 40 and thereby assist in removing the heat of reaction.
  • second feed exit stream 25 is recycled into reaction zone 11 via inlet 47.
  • the apparatus further comprises a catalyst 12 within the tubular reaction
  • the apparatus further comprises a catalyst bed(s) within the
  • interior conduit(s) 20 is concentric with the tubular reaction zone(s) 11.
  • the tubular reaction zone(s) 11 has a cross-section which is a substantially circular, interior conduit 20 is concentric with tubular reaction zone 11 and tubular reaction zone 11 comprises a catalyst bed 12 surrounding the interior conduit 20.
  • the apparatus of the invention comprises a plurality of injectors 30, preferably between 2 and 40 injectors, more preferably between 4 and 25 injectors and most preferred between 6 and 15 injectors.
  • injectors 30 are selected from the group consisting of wall penetrations, holes, perforations, spargers, or combinations thereof.
  • the apparatus further comprises a pressure drop control means 50 in conduit(s) 20 proximate to at least one of or each of injectors 30.
  • Pressure drop control means 50 can be packing, pellets or any other flow restricting devices.
  • Figure 6 illustrates an enlarged schematical representation of a pressure drop control means 50 (pellets) according to one embodiment of the invention.
  • Apparatus 60 comprises a fluidized bed reaction zone 55 having a height and having a first fluid reaction feed inlet 13 at a lower end for first fluid reaction feed 14 and a product outlet 15 for product stream 1 at an upper end.
  • the first fluid reaction feed 14 includes a first reactant and preferably a portion of second fluid reactant.
  • Fluidized bed reaction zone 55 also includes an interior conduit 20 extending vertically within the fluidized bed reaction zone 55, the conduit 20 having a multiplicity of injectors 30 spaced apart along the length of the conduit, each of the injectors 30 capable of introducing a controlled amount of a second fluid reaction feed 22 into the fluidized bed reaction zone 55.
  • conduit 20 also includes pressure drop control means 50 proximate injectors 30.
  • Second fluid reaction feed 22 preferably comprises a second reactant.
  • FIG. 8 Yet another embodiment of the invention, shown in Figure 8, relates to a continuous flow chemical reaction apparatus 70 comprising a plurality of fluidized bed reaction zones 55 within a heat transfer vessel 41 having at least one heat transfer zone 42, each of the heat transfer zones 42 having a heat transfer fluid inlet 43 and a heat transfer fluid outlet 44 and each of the tubular reaction zones 55 having a height.
  • the tubular reaction zones 55 also having a first fluid feed inlet 45 for first fluid feed 14 at a lower end, a product feed outlet 46 for product feed 16 at an upper end and an interior conduit 20 extending vertically within each of fluidized bed reaction zones 55.
  • the interior conduits 20 having a multiplicity of injectors 30 spaced apart along the length of the fluidized bed reaction zones 55 and each of the injectors 30 being adapted to introduce a controlled amount of a portion of second fluid feed reactant 22 into the fluidized bed reaction zone 55.
  • Figure 9 illustrates a partial schematical view of another embodiment of the invention where apparatus where second reactant feed 22 is introduced into a fluidized bed reaction zone 81 via conduits 82, wherein the conduits 82 are perpendicular to the flow of first reaction feed 14 and each conduit 82 introduces different or the same amounts of second reaction feed 22 at each point along reaction zone 81.
  • the fluidized bed apparatus is capable of operating in the bubbling regime.
  • the reaction zone is a circulating fluidized bed.
  • Another aspect of the invention relates to improved chemical reactions. Using the present invention, chemical reactions can be performed achieving improved yields and selectivity.
  • the fluid flowing through the distribution member can be a single reactant component, a mixture of reacting components or a mixture of reacting component(s) and inert
  • reaction product comprising:
  • Another embodiment of the invention relates to a method of performing a catalytic chemical reaction comprising reacting a first fluid reactant with a second fluid reactant to
  • a first fluid reaction feed is introduced into a first end of a tubular reaction zone having a length and containing the catalyst bed, the first fluid reaction feed containing the first and second fluid reactants flowing towards a second end of the tubular reaction zone;
  • a second fluid reaction feed containing the second reactant is introduced into a conduit within and concentric to the tubular reaction zone, the conduit having a multiplicity of injectors spaced apart lengthwise along it and each of the injectors introduces a controlled amount of the second reactant into the tubular reaction zone;
  • the tubular reaction zone(s) contains a catalyst and the first fluid reactant flows through the catalyst along with the second fluid reactant.
  • the chemical reaction has a selected reaction temperature and the temperature in the tubular reaction zone(s) is maintained within 15°C of the selected reaction temperature through at least 50% of the length of the tubular reaction zone(s).
  • the reaction temperature is maintained within 10°C, advantageously within 6°C of the selected reaction temperature through at least 50% of the length of the
  • tubular reaction zone(s) tubular reaction zone(s).
  • the chemical reaction has an explosive
  • the invention further comprises controlling the amount of the second fluid reactant introduced into the tubular reaction zone so that the concentration of the second fluid reactant is at least 70%, preferably at least 80%, more preferably at least 90%, of the explosive concentration through at least 50% of the length of the tubular reaction zone and does not exceed the explosive concentration at any point throughout the length of the
  • the total overall inventory of the reacting mixture falls within an unsafe/explosive composition region, while at any given point or region within the reactor the compositional mixture is within the domain of safe/non- explosive compositions.
  • the chemical reaction is the partial oxidation of ethane to ethylene and acetic acid, and wherein the first fluid reactant comprises ethane and the second fluid reactant comprises oxygen, (e.g., pure O 2 , air, etc.).
  • oxygen e.g., pure O 2 , air, etc.
  • the chemical reaction is the partial oxidation of ethane to ethylene and acetic acid, wherein the first fluid reactant comprises ethane and the second fluid reactant comprises oxygen, and at least 10% of the ethane in the first fluid reactant is reacted to form acetic acid per single pass through the tubular reaction zone.
  • Another embodiment relates to a method of performing a catalytic chemical reaction comprising reacting a first fluid reactant with a second fluid reactant to form a reaction product in a catalyst bed, wherein:
  • the second fluid reactant is introduced into a conduit within the fluidized bed reaction zone, the conduit having a multiplicity of injectors spaced apart lengthwise along it and each of the injectors introduces a controlled amount of the second reactant into the fluidized bed reaction zone;
  • the chemical reaction in the fluidized bed proceeds in the- bubbling regime.
  • a full range of industrially important reactions can benefit from the current inventions especially those suffering from: temperature run-away limitations and explosive mixtures composition limitation such as ethylene oxide, maleic anhydride, phalic anhydride, etc. Additional reactions which may be performed using the present invention are set forth in Table I below.
  • Example 1 The invention is further described in the following examples.
  • the examples are illustrative of some of the products and methods of making the same falling within the scope of the present invention. They are, of course, not to be considered in any way limitative of the invention. Numerous changes and modifications can be made with respect to the invention.
  • Example 1 Example 1:
  • Model equations have been developed for the catalyst tube resulting in a system of non-linear ordinary differential equations which were solved numerically to predict the non- isothermal behavior of the reaction. This is to calculate the reacting mixture compositions, pressure and temperature at each point along the length of the reactor tube.
  • the model was then used to simulate operating scenarios where the target in each one was to maximize the production of ethylene and acetic acid without having a oxygen concentration higher than that of the lower explosion limit of the ethane-oxygen mixture (estimated as 8% oxygen in ethane under the elected operating conditions).
  • Operating variables and design parameters for the three cases (Cases I, II and III) which were studied using the model are provided in Table II.
  • the predicted performance is
  • the second scenario employs a reactor of the type proposed by Tonkovich et al. (1996) in Chem. Eng. Science, vol. 51, in which the distribution of more oxygen than that allowed in the main feed is carried out continuously along the catalyst bed by means of a porous central tube. The amount of oxygen flowed through the central tube was limited by the oxygen concentration at intermediate points in the catalyst bed.
  • the third scenario (Case III) has a special oxygen flow distribution pattern, as shown in Figure 10.
  • the same constraint of 8% oxygen concentration was used for this case.
  • the invention provides for better control over the catalyst bed temperature as shown in Figure 11 , maintaining the catalyst and reaction mixture in a preferred operating temperature range, while this advantage was not achievable neither by conventional reactor nor by the uniform distribution option.
  • the feed section consisted mainly of clusters of compressed gas cylinders with manifolds and mass flow controllers.
  • the feed section was constructed to feed into the reactor the following reactants: ethane, air, oxygen, carbon dioxide and nitrogen.
  • Mass flow controllers on each gas feed line were operated from a remote location.
  • a forward pressure regulator on each gas feed line maintained the desired pressure of the reactants.
  • the prototype multi-injection reactor was constructed from 316 stainless steel with a length of 12.5 m. It was bent into a U-shape to keep the structure within a reasonable height.
  • the reactor consisted of an inner (distribution) tube, a thermowell, an outer tube and a shell. The inner tube and the thermowell were situated inside the outer tube, which was filled with a
  • the inner tube had distribution points along its length equipped with custom-built injectors.
  • the size and number of injector holes were designed to provide the following flow pattern:
  • DPT differential pressure transmitter
  • the product gases from the reactor were then transferred to a shell and tube heat exchanger, where product condensation was achieved by a chilled water being circulated on the shell side.
  • the two phase flow exiting the exchanger was sent to a gas liquid separator, from which gases were vented and liquids were collected in a receiving tank. Both condensation and separation of the product took place under the system pressure by means of a back pressure regulator installed on the vent gas line leaving the condensate separator.
  • the heat transfer system included a steam drum and an air blower.
  • the steam drum was located at a point above the reactor and was connected to the shell side of the reactor.
  • the air blower was connected to the jacket of the drum to cool the steam.
  • the system was instrumented with a level transmitter to indicate the level of water in the drum, a temperature transmitter, a pressure transmitter and safety relief valve.
  • the present invention provides a productivity to acetic acid at least 80% greater than the productivity provided by the comparative embodiment (Run #2). Moreover, both the ethane conversion and acetic acid selectivity is improved using the invention.

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AT01931244T ATE468914T1 (de) 2000-05-05 2001-05-04 Vorrichtung zur kontrollierten und optimierten zugabe von reaktanten in ein kontinuierliches strömungssystem und verfahren zu dessen gebrauch
DE60142229T DE60142229D1 (de) 2000-05-05 2001-05-04 Vorrichtung zur kontrollierten und optimierten zugabe von reaktanten in ein kontinuierliches strömungssystem und verfahren zu dessen gebrauch
EP01931244A EP1284815B1 (en) 2000-05-05 2001-05-04 An apparatus for the controlled optimized addition of reactants in continuous flow reaction systems and methods of using the same
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CN109476564A (zh) * 2016-07-26 2019-03-15 国际壳牌研究有限公司 乙烷的氧化脱氢(odh)
EA038258B1 (ru) * 2016-07-26 2021-07-30 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Окислительное дегидрирование (одг) этана
CN109476564B (zh) * 2016-07-26 2021-08-13 国际壳牌研究有限公司 乙烷的氧化脱氢(odh)
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US11161085B2 (en) 2017-04-27 2021-11-02 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Fluidized bed device and method for preparing para-xylene and co-producing light olefins from methanol and/or dimethyl ether and benzene
US11180431B2 (en) 2017-04-27 2021-11-23 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Fluidized bed device and method for preparing para-xylene and co-producing light olefins from methanol and/or dimethyl ether and toluene
EP3616782A4 (en) * 2017-04-27 2020-05-13 Dalian Institute Of Chemical Physics, Chinese Academy of Sciences FLUIDIZED BED DEVICE AND PROCESS FOR PREPARING P-XYLENE AND CO-PRODUCING LOW CARBON OLEFINS FROM METHANOL AND / OR DIMETHYL ETHER AND BENZENE
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GC0000225A (en) 2006-03-29
US7445758B2 (en) 2008-11-04
KR100742842B1 (ko) 2007-07-25
DE60142229D1 (de) 2010-07-08
KR20030022116A (ko) 2003-03-15
EP1541226A3 (en) 2006-05-17
ATE468914T1 (de) 2010-06-15
WO2001085333A3 (en) 2002-09-06
ES2345535T3 (es) 2010-09-27
EP1541226A2 (en) 2005-06-15
US20060003402A1 (en) 2006-01-05
US6977064B1 (en) 2005-12-20
AU2001258079A1 (en) 2001-11-20
EP1284815B1 (en) 2010-05-26
EP1284815A2 (en) 2003-02-26
GC0000413A (en) 2007-03-31

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